Organic-inorganic hybrids based on monovacant Keggin-type polyoxotungstates and 3d-4f heterometals

Hai Yan Zhao; Jun Wei Zhao; Bai Feng Yang; Huan He; Guo Yu Yang

doi:10.1039/c3ce41007b

Organic-inorganic hybrids based on monovacant Keggin-type polyoxotungstates and 3d-4f heterometals

Hai Yan Zhao, Jun Wei Zhao^*, Bai Feng Yang, Huan He, Guo Yu Yang

^*此作品的通讯作者

化学与化工学院

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37 引用（Scopus）

摘要

Four organic-inorganic hybrid monolacunary Keggin polyoxotungstate-based 3d-4f heterometallic derivatives [Cu(en)₂(H₂O)] ₂[Tb(α-HSiW₁₁O₃₉)(H₂O) ₃]·12H₂O (1), [Cu(en)₂(H ₂O)]₂[Eu(α-HGeW₁₁O₃₉) (H ₂O)₃]·12H₂O (2), Na₂[Cu(en) ₂(H₂O)]₄[Sm(α-PW₁₁O ₃₉)(CH₃COO)(H₂O)]₂·10H ₂O (3) and [Cu(en)₂ (H₂O)]₅[Cu(en) ₂][Tb(α-GeW₁₁O₃₉)(CH₃COO) (H₂O)]₂·14H₂O (4) (en = ethylenediamine) have been hydrothermally prepared and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. 1 and 2 are isomorphic and exhibit the interesting one-dimensional chain arrangements built by monovacant-lanthanide substituted Keggin-type [Ln(α-HXW₁₁O₃₉)(H₂O)₃] ^4- (Ln = Tb^III, Eu^III; X = Si^IV, Ge^IV) units via W-O-Ln-O-W bridges whereas 3 and 4 display typical organic-inorganic hybrid dimeric structures consisting of [(α-XW ₁₁O₃₉)Ln(H₂O)(η²,μ-1,1)- CH₃COO]₂^10/12- units modified by [Cu(en) ₂(H₂O)]²⁺ fragments. To the best of our knowledge, 1 and 2 represent the rare 1D chain-like monovacant Keggin-type 3d-4f heterometallic polyoxotungstates containing both unusual 1:1 [Ln(α-XW₁₁O₃₉)]^4/5- units and en ligands, whereas 3 and 4 represent the first monovacant Keggin-type phosphotungstates or germanotungstates containing both 3d-4f heterometals and mixed ligands of en and acetate. Furthermore, the variable-temperature magnetic susceptibilities of 1 and 3 have been investigated.

源语言	英语
页（从-至）	8186-8194
页数	9
期刊	CrystEngComm
卷	15
期	40
DOI	https://doi.org/10.1039/c3ce41007b
出版状态	已出版 - 28 10月 2013

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@article{b09fe335e6e641629822476e09e2e571,

title = "Organic-inorganic hybrids based on monovacant Keggin-type polyoxotungstates and 3d-4f heterometals",

abstract = "Four organic-inorganic hybrid monolacunary Keggin polyoxotungstate-based 3d-4f heterometallic derivatives [Cu(en)2(H2O)] 2[Tb(α-HSiW11O39)(H2O) 3]·12H2O (1), [Cu(en)2(H 2O)]2[Eu(α-HGeW11O39) (H 2O)3]·12H2O (2), Na2[Cu(en) 2(H2O)]4[Sm(α-PW11O 39)(CH3COO)(H2O)]2·10H 2O (3) and [Cu(en)2 (H2O)]5[Cu(en) 2][Tb(α-GeW11O39)(CH3COO) (H2O)]2·14H2O (4) (en = ethylenediamine) have been hydrothermally prepared and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. 1 and 2 are isomorphic and exhibit the interesting one-dimensional chain arrangements built by monovacant-lanthanide substituted Keggin-type [Ln(α-HXW11O39)(H2O)3] 4- (Ln = TbIII, EuIII; X = SiIV, GeIV) units via W-O-Ln-O-W bridges whereas 3 and 4 display typical organic-inorganic hybrid dimeric structures consisting of [(α-XW 11O39)Ln(H2O)(η2,μ-1,1)- CH3COO]210/12- units modified by [Cu(en) 2(H2O)]2+ fragments. To the best of our knowledge, 1 and 2 represent the rare 1D chain-like monovacant Keggin-type 3d-4f heterometallic polyoxotungstates containing both unusual 1:1 [Ln(α-XW11O39)]4/5- units and en ligands, whereas 3 and 4 represent the first monovacant Keggin-type phosphotungstates or germanotungstates containing both 3d-4f heterometals and mixed ligands of en and acetate. Furthermore, the variable-temperature magnetic susceptibilities of 1 and 3 have been investigated.",

author = "Zhao, {Hai Yan} and Zhao, {Jun Wei} and Yang, {Bai Feng} and Huan He and Yang, {Guo Yu}",

year = "2013",

month = oct,

day = "28",

doi = "10.1039/c3ce41007b",

language = "English",

volume = "15",

pages = "8186--8194",

journal = "CrystEngComm",

issn = "1466-8033",

publisher = "Royal Society of Chemistry",

number = "40",

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TY - JOUR

T1 - Organic-inorganic hybrids based on monovacant Keggin-type polyoxotungstates and 3d-4f heterometals

AU - Zhao, Hai Yan

AU - Zhao, Jun Wei

AU - Yang, Bai Feng

AU - He, Huan

AU - Yang, Guo Yu

PY - 2013/10/28

Y1 - 2013/10/28

N2 - Four organic-inorganic hybrid monolacunary Keggin polyoxotungstate-based 3d-4f heterometallic derivatives [Cu(en)2(H2O)] 2[Tb(α-HSiW11O39)(H2O) 3]·12H2O (1), [Cu(en)2(H 2O)]2[Eu(α-HGeW11O39) (H 2O)3]·12H2O (2), Na2[Cu(en) 2(H2O)]4[Sm(α-PW11O 39)(CH3COO)(H2O)]2·10H 2O (3) and [Cu(en)2 (H2O)]5[Cu(en) 2][Tb(α-GeW11O39)(CH3COO) (H2O)]2·14H2O (4) (en = ethylenediamine) have been hydrothermally prepared and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. 1 and 2 are isomorphic and exhibit the interesting one-dimensional chain arrangements built by monovacant-lanthanide substituted Keggin-type [Ln(α-HXW11O39)(H2O)3] 4- (Ln = TbIII, EuIII; X = SiIV, GeIV) units via W-O-Ln-O-W bridges whereas 3 and 4 display typical organic-inorganic hybrid dimeric structures consisting of [(α-XW 11O39)Ln(H2O)(η2,μ-1,1)- CH3COO]210/12- units modified by [Cu(en) 2(H2O)]2+ fragments. To the best of our knowledge, 1 and 2 represent the rare 1D chain-like monovacant Keggin-type 3d-4f heterometallic polyoxotungstates containing both unusual 1:1 [Ln(α-XW11O39)]4/5- units and en ligands, whereas 3 and 4 represent the first monovacant Keggin-type phosphotungstates or germanotungstates containing both 3d-4f heterometals and mixed ligands of en and acetate. Furthermore, the variable-temperature magnetic susceptibilities of 1 and 3 have been investigated.

AB - Four organic-inorganic hybrid monolacunary Keggin polyoxotungstate-based 3d-4f heterometallic derivatives [Cu(en)2(H2O)] 2[Tb(α-HSiW11O39)(H2O) 3]·12H2O (1), [Cu(en)2(H 2O)]2[Eu(α-HGeW11O39) (H 2O)3]·12H2O (2), Na2[Cu(en) 2(H2O)]4[Sm(α-PW11O 39)(CH3COO)(H2O)]2·10H 2O (3) and [Cu(en)2 (H2O)]5[Cu(en) 2][Tb(α-GeW11O39)(CH3COO) (H2O)]2·14H2O (4) (en = ethylenediamine) have been hydrothermally prepared and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. 1 and 2 are isomorphic and exhibit the interesting one-dimensional chain arrangements built by monovacant-lanthanide substituted Keggin-type [Ln(α-HXW11O39)(H2O)3] 4- (Ln = TbIII, EuIII; X = SiIV, GeIV) units via W-O-Ln-O-W bridges whereas 3 and 4 display typical organic-inorganic hybrid dimeric structures consisting of [(α-XW 11O39)Ln(H2O)(η2,μ-1,1)- CH3COO]210/12- units modified by [Cu(en) 2(H2O)]2+ fragments. To the best of our knowledge, 1 and 2 represent the rare 1D chain-like monovacant Keggin-type 3d-4f heterometallic polyoxotungstates containing both unusual 1:1 [Ln(α-XW11O39)]4/5- units and en ligands, whereas 3 and 4 represent the first monovacant Keggin-type phosphotungstates or germanotungstates containing both 3d-4f heterometals and mixed ligands of en and acetate. Furthermore, the variable-temperature magnetic susceptibilities of 1 and 3 have been investigated.

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Organic-inorganic hybrids based on monovacant Keggin-type polyoxotungstates and 3d-4f heterometals

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